Self-arrayed hole-carryable polymers used for organic photo-refractive materials and photo-refractive mixture containing them

ABSTRACT

A novel self-arrayed hole-carryable polymer having rigid backbone of high-ordered self-orienting layer structure, i.e. polyester, polyamide or biphenyl series polyester and flexible side chain, i.e. carbazole derivatives inducing hole-carryable characteristic group and exhibiting high thermo-stability, plain processibility and high photoconductivity; and A photo-refractive material comprising the photo-refractive material, charge producer and nonlinear optical characteristic group as electro-optical material and exhibiting enhanced photoconductivity without adding plasticizer.

CROSS REFERENCE TO RELATED APPLICATION

[0001] This application claims the benefit of Korean Patent ApplicationNo. 2002-10432, filed on Feb. 27, 2002 in Korea, which is herebyincorporated by reference for all purposes as if fully set forth herein.

BACKGROUND OF THE INVENTION

[0002] 1. Field of the Invention

[0003] The present invention relates to novel self-arrayed polymers andmore particularly, to self-arrayed polymers with an excellenthole-carryable property and mixtures for manufacturingphoto-refractive/photo-breaking elements containing them as ahole-carryable material.

[0004] 2. Description of the Related Art

[0005] Conventionally polymers, such as poly (p-phenylenevinylene)(hereinafter referred to PPV), polythiophene, polyvinylcarvazole(hereinafter referred to PVK) and the like, and tertiary aminederivatives such as tetraphenylbiphenyldiamine (hereinafter referred toTPD) or TPD species were mainly used as organic hole-carryablematerials. But it happened problems of low thermo-stability andrecrystallization resulted from using TPD and its derivatives as ahole-carryable material because of their low glass transition points.

[0006] Also, the process for adding electro-optical pigments into themedium of photoconductive polymer was mainly used, as organicphoto-refractive material, for utilizing hole-carryable photoconductivepolymers. At this time, PVK or polysilane was typically used aspolymers. But, Polymers such as PKV has a disadvantage of badprocessability and low photo-refraction efficiency resulting from highglass transition point of over 200° C. To overcome this problem, itdeveloped process for using plasticizers and additives for enhancing thephoto-refraction efficiency by lowing glass transition point less thanroom temparature.

[0007] But said process had also serious problem of phase isolationowing to added plasticizers and of low relative electro-chemicalcharacteristic groups and concentration of hole-carriers, which resultedin low photo-refraction efficiency.

[0008] For the foregoing reasons, there is a need for hole-carryablepolymer with high glass transition point, thermo-stability that can beeasily processed.

SUMMARY OF THE INVENTION

[0009] The present invention is directed to a hole-carryable polymerthat substantially satisfies the need.

[0010] An object of the present invention is to provide a novelhole-carryable polymer having self hole-carryability and excellentmechanical, thermal properties. The polymer has a rigid backbone ofhigh-ordered self-orienting layer structure and flexible side chainwhich inducing hole-carryable characteristic group. As a result, thepolymer has high thermo-stability originated from rigid backbone andplain processability and fast reactivity and high photoconductivitybased upon low glass transition point (T_(g)) originated from flexibleside chain.

[0011] Another object of the present invention is to provide aphoto-refractive mixture having said polymer with excellentphotoconductivity and low Tg. Accordingly, the mixture has high contentsof electro-optical characteristic group and excellent photo refractivitywithout adding plasticizer.

[0012] In a first aspect, the present invention provides a Self-arrayedpolymer exhibiting hole-carryability and formula 1 below:

[0013] [Formula 1]

[0014] wherein A is a chromophore (hole-carryable characteristic group),which is selected from the compound showing in Formula 2 or Formula 3below:

[0015] [Formula 2]

[0016] wherein R₁ is selected from the group of —O—(CH₂)_(q)— (q is aninteger from 1 to 20), —S—(CH₂)_(m)— (m is an integer from 1 to 20),

[0017] (n is an integer from 1 to 5) or

[0018] (p is an integer from 1 to 5); and

[0019] [Formula 3]

[0020] wherein R₂ is selected from the group of —O—(CH₂)_(v)—O— (v is aninteger from 1 to 20), —S—(CH₂)_(w)—S— (w is an integer from 1 to 20),

[0021]  (n is an integer from 1 to 5) or

[0022]  (p is an integer from 1 to 5):

[0023] r is an integer from 3 to 300 as polymerization degree:

[0024] X is selected from

[0025]  and

[0026] M is a selected from 1) to 4) below as a co-monomer.

[0027] 1)

[0028]  (wherein B is H, Cl, Br or CH₃);

[0029] 2)

[0030]  (wherein said compound is 1,1′-, 2,2′-, 3,3′-, 4,4′-, 1,3′-,1,2′-, 2,3′-, 2,4′- or 3,4′-biphenyl series isomers);

[0031] 3)

[0032]  (wherein said compound is 1,4-, 1,5-, 1.6-, 1,7-, 2,3-, 2,5-,2,6- or 2,7-naphthalene series isomers); and

[0033] 4)

[0034]  (wherein Y is O, CH₂, SO₂, S,

[0035] In another aspect, the present invention provides aphoto-refractive mixture using host-guest series, which dispersingcharge-producer and elctro-optical material as being medium of theself-arrayed polymers.

[0036] These and other features, aspects, and advantages of the presentinvention will become better understood with reference to the followingdescription and appended claims.

BRIEF DESCRIPTION OF THE DRAWINGS

[0037] The accompanying drawings, which are included to provide afurther understanding of the invention and are incorporated in andconstitute a part of this specification, Illustrate embodiments of theinvention and together with the description serve to explain theprinciples of the invention

[0038] In the drawings:

[0039]FIG. 1 is a graph showing absorbance spectrum in the field of UVand visible light for polyester synthesized in Example 4 of the presentinvention;

[0040]FIG. 2 is a graph comparing the photoconductivity of photo elementmanufactured in Example 7 of the present invention with that of photoelement in prior art;

[0041]FIG. 3 is a graph showing RXD analysis result of polyester andphoto-refractive mixture manufactured in Example 8 of the presentinvention; and

[0042]FIG. 4 is a graph illustrating the measurement result ofphoto-breaking effect for the photo-refractive mixture of the presentinvention according to Example 9 of the present invention.

DETAILED DESCRIPTION OF THE ILLUSTRATED EMBODIMENTS

[0043] Reference will now be made in detail to the illustratedembodiment of the present invention, which is illustrated in theaccompanying drawings.

[0044] The novel hole-carryable polymer of the present invention iscomposed of the repeat-unit structure shown in formula 1 below:

[0045] [Formula 1]

[0046] wherein A is a chromophore (hole-carryable characteristic group),which is selected from the compound shown in Formula 2 or Formula 3below:

[0047] [Formula 2]

[0048] wherein R₁ is —O—(CH₂)_(q)— (q is an integer from 1 to 20),—S—(CH₂)_(m)— (m is an integer from 1 to 20),

[0049]  (n is an integer from 1 to 5) or

[0050]  (p is an integer from 1 to 5); and

[0051] [Formula 3]

[0052] wherein R₂ is —O—(CH₂)_(v)—O— (v is an integer from 1 to 20),—S—(CH₂)_(w)—S— (w is an integer from 1 to 20),

[0053]  (n is an integer from 1 to 5) or

[0054]  (p is an integer from 1 to 5):

[0055] r is an integer from 3 to 300 as polymerization degree:

[0056] X is selected from

[0057]  and

[0058] M is a selected from the group composed of 1) to 4) below as aco-monomer.

[0059] 1)

[0060]  (wherein B is H, Cl, Br or CH₃);

[0061] 2)

[0062]  (wherein said compound is 1,1′-, 2,2′-, 3,3′-, 4,4′-, 1,3′-,1,2′-, 2,3′-, 2,4′- or 3,4′-biphenyl series isomers);

[0063] 3)

[0064]  (wherein said compound is 1,4-, 1,5-, 1.6-, 1,7-, 2,3-, 2,5-,2,6- or 2,7-naphthalene series isomers); and

[0065] 4)

[0066]  (wherein Y is O, CH₂, SO₂, S,

[0067] Following is a representative description of synthesis process ofpolymer comprising 2,5-di[(N-carbazole)dekyl]terephthalic acid amongself-arrayed polymers shown in above Formula 1.

[0068] Carbazole(I) and 1,10-dibromodecane(II), which is flexiblematrix, is reacted to synthesize (N-carbazole)-10-bromodecane(III),which was reacted into diethyl-2,5-dihydroxy-terephthalate(IV) tosynthesize diethyl-2,5-di[(N-carbazole)decyl]terephthalate(V).Diethy10-2,5-[(N-carbazole)decyl] terephthalate(V) was refluxed in basicsolution and treated with acid to produce the final product,2,5,-di[(N-carbazole)decyl]terephthalic acid(VI).

[0069] The above-mentioned synthesis process is shown briefly in thefollowing Reaction 1 to Reaction 3.

[0070] wherein R is

[0071]  and

[0072] q is an integer from 0 to 20.

[0073] Polyester(VII), polyamide(VIII) and biphenyl seriespolyester(IX), which are polymers of the present invention, aresynthesized plainly from said compound(VI) following Reaction 4, 5 and 6respectively.

[0074] wherein reaction 4 to 6, R is

[0075] (q is an integer from 0 to 20); and r is an integer from 3 to 300as polymerization degree.

[0076] The said polymers capable of synthesizing in the presentinvention have a number average molecular weight in the range of 2,000to 240,000.

[0077] Polymers in the present invention does not make hole-carryablecharacteristic group crystallize in spite of exceedingly highconcentration of the group and have high solubility in organic solvents.So, it is possible to manufacture film with optically excellent physicalproperties. Also the polymers show remarkably high photoconductivityresulted from their excellent hole-carryable property.

[0078] The present invention provides charge producer as being mediumlike said polymers and photo-refractive mixtures using host-guest systemmaking electro-optical materials dispersed.

[0079] Specifically, we identified 4-fold photoconductivity, on dopingthe mixtures about 1% by making hole-carryable polymers shown aboveFormula 1 be medium and by using C₆₀ shown in Formula 4 or TNF(trinitro-fluoren-9-one) shown in Formula 5 as charge producer, as highas using the conventional PVK. This is extremely high value amongphotoconductivity of hole-carryable polymers known until present.

[0080] [Formula 4]

[0081] [Formula 5]

[0082] High photoconductivity of polymers of the present invention iscaused by the fact that the polymers have high-ordered self-arrayedlayer structures by inducing flexible side chains with hole-carryablemolecule into rigid backbone, on the other hand typical hole-carryablepolymers have amorphous structure. On adding electro-optical pigmentsinto these layer structures, which causes local concentration ofhole-carryalbe material to be increased and to enhance hole-carriabilityby self-array of polymers, they show high photoconductivity. Also, highglass transition point of backbone make stability of elements increaseand low glass transition point of side chain devises processability andfast reactivity in processability and stability.

[0083] Also, the polymers of the present invention have an excellenthole-carryability in themselves and as a result can be usedhole-carryable layer of the organic fluorescent elements or variousoptical elements.

[0084] Besides, by using said polymers with high photoconductivity ofthe present invention, without adding other plasticizers we canmanufacture photo-refractive mixtures, which have low glass transitionpoint but does not have phase isolation, showing excellent stability,fast reaction rate and high photo-refractive property.

[0085] The photo-refractive mixtures of the present invention can bemanufactured by making the photo-conductive polymers shown in aboveFormula 1 be medium and by using host-guest system addingnonlinear-optical characteristic group (electro-optical material) andcharge producer.

[0086] At this time, we can use general nonlinear-optical characteristicgroup (electro-optical material) shown in following Formula 6 as annonlinear-optical characteristic group and use compounds in aboveFormula 4 or 5 as charge producer.

[0087] [Formula 6]

[0088] wherein R₁ is (C₁-C₁₀) alkyl, (C₁-C₁₀) alkyl substituted withhydroxyl group to terminal end or (C5-C10) cycloalkyl; R₂ is nitro groupor dicyanovinyl group.

[0089] The photo-refractive elements of the present invention can bemanufactured by dissolving mixture comprising of photo-conductivepolymers, nonlinear-optical characteristic group (electro-opticalmaterial) and charge producer in ordinary use solvents, after droppingrespectively the solution into glass coated two sheets of ITO (IndiumTin Oxide) electrode then heating to remove the solvents, and aftermanufacturing two electrodes with a thickness of 100 μm by puttingtogether said two sheets of glass applied polymers then by connecting anelectric line to these two sheets of ITO electrode.

[0090] The photo-refractive mixtures manufactured following said processmaintained layer structure with high-ordered self-orientation afterdoping lots of amount of nonlinear chromophore and the like. Elementsusing these mixtures, which have a side chain with low glass transitionpoint, were stabilized after manufacturing them 6 months withoutproblems of phase isolation or crystallization, which stability resultedfrom stability of rigid backbone and not having additives such asplasticizer. Besides, low glass transition point under room temparatureshowing in side chains provided high photo-refraction and reaction rate.As a result of analysis of the photo-refraction efficiency with two-beamcoupling, we obtained high gains factor of 200 cm⁻¹ (50 V/μm).Consequently, it can be applied to the field of photo-image processing,photo-information processing, image transmission and the like byutilizing elements using these mixtures.

[0091] Also, It happened fanning phenomenon of dispersing over 65% ofirradiated light on applying an electric field to the elements usingsaid photo-refractive mixtures and then irradiating light. The strongerthe intensity of light, the faster the phenomenon and the stronger theintensity of electric field, the higher fanning value. Accordingly, thephoto-refractive mixtures can be used photo-breaking elements breakablethe irradiated light.

[0092] We provide desirable examples to help understanding of thepresent invention. But below examples is provided for understanding moreeasily, the present invention is not limited the examples.

EXAMPLE 1 Synthesis of (N-carbazol)-10-bromodecane(III) (Reaction 1)

[0093] In this example, we synthesized (N-carbazol)-10-bromodecane shownin Reaction 1, wherein q is 9, like following.

[0094] Into a 3-necked flask was placed carbazol 5.0 g (0.0299 mol) thepresence of nitrogen current and dissolved in 50% NaOH aqueous solution.Benzene 15 ml and BTEAC (benzyltriethylammonium chloride) 0.25 g wasadded and dibromodecane 100 g was added into it slowly. After reactingsaid reactants at room temperature for 24 hours and extracting theproduct in water and methylenechloride, by separating and drying throughcolumn chromatography using mixed solvent (20/1 V/V) of hexane and ethylacetate, (N-carbazol)-10-bromodecane was synthesized (80% yield).

[0095] The obtained product was analyzed by using NMR/IR and followingis the analysis result.

[0096]¹H-NMR [CDCl₃, ppm]: 8.2 (d, 2H), 7.5-7.2 (m, 6H), 4.3 (t, 2H),3.4 (t, 2H), 2.0-1.8 (m, 4H), 1.6-1.3 (m, 12H)

[0097] IR [cm⁻¹ ]: 3,100-3,000 (aromatic C—H), 2,960-2,900 (aliphaticC—H), 1,350-1,000 (C—N), 750, 700 (aromatic OOP)

EXAMPLE 2 Synthesis of diethyl-2,5-di[(N-carbazol)decyl]terephthalate(V) (Reaction

[0098] In this example, we synthesizeddiethyl-2,5-di[(N-carbazol)decyl]terephthalate (V) shown in Reaction 2like following.

[0099] Into a 250 ml, 3-necked flask was placed K₂CO₃ 1.2 g (0.009 mol)and diethyl-2,5-dihydroxy terephthalate 1.14 g (0.0045 mol). After themixture is dissolved in DMF (dimethylformate) 30 ml,(N-carbazol)-10-bromodecane 4 g (0.01 mol) produced in said example 1was added. After heating the reacting solution at 50° C. and reacting 24hours, filtered the solution to remove K₂CO₃ and vacuum distilled toremove DMF. By separating and drying pale-brown product through columnchromatography using missed solvent of hexane and ethyl acetate (10/1V/V), diethyl-2,5-di[(N-carbazol)decyl] terephthalate was synthesized(90% yield).

[0100] The obtained product was analyzed by using NMR/IR and followingis the analysis result.

[0101]¹H-NMR [CDCl₃, ppm]: 8.1 (d, 4H), 7.5-7.2 (m, 14H), 4.3 (m, 8H),4.0 (t, 4H), 2.0-1.7 (m, 8H), 1.5-1.2 (m, 30H)

[0102] IR [cm⁻¹]: 3,100-3,000 (aromatic C—H), 2,960-2,900 (aliphaticC—H), 1,750 (C═O), 1,350-1,000 (C—N), 750, 700 (aromatic OOP)

EXAMPLE 3 Synthesis of 2,5-di[(N-carbazol)decyl]terephthalic acid (VI)(Reaction 3)

[0103] In this example, we synthesized2,5-di[(N-carbazol)decyl]terephthalte(VI) shown in Reaction 3 likefollowing.

[0104] Diethyl-2,5-di[(N-carbazol)decyl]teephthalate 3.23 g (0.0037 mol)produced in the above Example was added in ethanol 100 ml and heated.Into this was placed ethanol 30 ml dissolved KOH 0.84 g and refluxed for6 hrs. After completing reaction, the mixtures were distilled underreduced pressure to remove ethanol, the resulting produced white soliddissolved in water and acidified in 2N HCl. By extracting this productwith methylene glycol and recrystallizing with ethanol, pure2,5-di[(N-carbazol)decyl]terephthalic acid was obtained (90% yield).

[0105] The obtained product was analyzed by using NMR/IR and followingis the analysis result.

[0106]¹H-NMR [CDCl₃, ppm]: 11.0 (s, 2H), 8.1 (d, 4H), 7.8 (s, 2H),7.5-7.2 (m, 12H), 4.4-4.2 (m, 8H), 2.0-1.7 (m, 8H), 1.5-1.2 (m, 24H)

[0107] IR [cm⁻¹]: 3,600-2,400 (—OH), 3.100-3,000 (aromatic C—H),2.960-2900 (aliphatic C—H), 1,750 (C═O), 1,350-1,000 (C—N), 750, 700(aromatic OOP)

EXAMPLE 4 Synthesis of Polymer Polyester (VII) (Reaction 4)

[0108] In this example, we synthesized polyester (VII) polymers shown inReaction 4 like following.

[0109] After displacing the interior of a 1000 ml, 3-necked round-bottomflask with nitrogen current, into this flask was placed2,5-di[(N-carbazol)decyl]terephthalic acid 7.1 g (0.00877 mol) producedin the above example 3. After dissolving the2,5-di[(N-carbazol)decyl]terephthalic acid in pyridine 80 ml, DPCP(diphenylcyclopropenone) 6.1 g (0.023 mol) and LiCl 0.7 g (0.02 mol)were added. After stirring the solution at 90° C. for 30 minutes,pyridine 100 ml dissolved hydroquinone 0.96 g (0.0087 mol) was addedinto it.

[0110] After reacting the solution at 90° C. for 6 hours and completingthe reaction, the solution was poured in excessive methanol to giveprecipitate. After filtrating the precipitate and washing it severallywith methanol and distilled water, by drying it in vacuum oven at 60° C.polyester was produced (99% yield).

[0111] The obtained product was analyzed by using NMR/IR and followingis the analysis result.

[0112]¹H NMR [CDCl₃, ppm]: 8.1 (d, 4H) 7.6-7.2 (m, 18H), 4.3 (t, 4H),4.1 (m, 4H), 2.0-1.7 (m, 8H), 1.5-1.2 (m, 24H)

[0113] IR [cm⁻¹]: 3,100-3,000 (aromatic C—H), 2,960-2,900 (aliphaticC—H), 1,750 (C═O), 1,350-1,000 (C—N), 820 (para-aromatic OOP)

[0114] The said produced polyester polymers have a glass transitionpoint of 28.6° C. and number weight molecular weight of over 100,000.And absorption spectrum of UV and visible light for the said polymers isshown in FIG. 1.

EXAMPLE 5 Synthesis of Polymer Polyamide (VII) (Reaction 5)

[0115] In this example, we synthesized polyamide (VII) polymer shown inReaction 5 like following.

[0116] After displacing the interior of a 1000 ml, 3-necked round-bottomflask with nitrogen current, into the flask were placed2,5-di[(N-carbazol)decyl]terephthalic acid 7.1 g (0.0087 mol) and CaCl₂6 g. The mixture was dissolved in NMP (N-methyl-2-pyrrolidone) 80 ml andpyridine 9 ml and then paraphenyldiamine 0.94 g (0.0087 mol) was added.Into the solution was added slowly P(Oph₃)₃ 5.4 g (0.017 mol) at roomtemperature and reacted at 90° C. for 2 hrs. After completing thereaction, the reaction solution was poured in excessive methanol to giveprecipitate. After filtrating the precipitate and washing it severallywith methanol and distilled water, by drying it in vacuum oven polyamidewas produced (98% yield).

[0117] The obtained product was analyzed by using NMR/IR and followingis the analysis result.

[0118]¹H-NMR [CDCl₃, ppm]: 8.1 (d, 4H), 7.6-7.2 (m, 18H), 4.3 (t, 4H),4.1 (m, 4H), 2.0-1.7 (m, 8H), 1.5-1.2 (m, 24H)

[0119] IR [cm⁻¹]: 3,440 (N—H), 3,100-3,000 (aromatic C—H), 2,960-2,900(aliphatic C—H), 1,750 (C═O), 1,350-1,000 (C—N), 820 (para-aromatic OOP)

EXAMPLE 6 Synthesis of Biphenyl Series Polymer Polyester(IX) (Reaction6)

[0120] In this example, we synthesized biphenyl series polymerpolyester(IX) in shown Reaction 6 like following.

[0121] After displacing the interior of a 1000 ml, 3-necked round-bottomflask with nitrogen current, into the flask was placed2,5-di[(N-carbazol)decyl]terephthalic acid 7.1 g (0.0087 mol) producedin Example 3. After dissolving the acid pyridine 80 ml, DPCP 6.1 g(0.023 mol) and LiCl 0.7 g (0.02 mol) were added. After stirring thereaction solution at 90° C. for 30 min. pyridine 100 ml dissolved4,4′-biphenol 1.63 g (0.0087 mol) was added into it. After reacting thesolution at 90° C. for 24 hours and completing the reaction, thereaction solution was poured into excessive methanol to giveprecipitate. After filtrating the precipitate and washing it severallywith methanol and distilled water, by drying it in vacuum oven biphenylseries polyester was produced (99% yield).

[0122] The obtained product was analyzed by using NMR/IR and followingis the analysis result.

[0123]¹H-NMR [CDCl₃, ppm]: 8.1 (d, 4H), 7.6-6.6 (m, 22H), 4.3 (t, 4H),4.1 (m, 4H), 2.0-1.7 (m, 8H), 1.5-0.1.2 (m, 24H)

[0124] IR [cm⁻¹]: 3,100-3,000 (aromatic C—H), 2,960-2,900 (aliphaticC—H), 1,750 (C═O), 1,350-1,000 (C—N), 820 (para-aromatic OOP)

EXAMPLE 7 Manufacture of Mixture and Element for MeasuringPhotoconductivity

[0125] In this example, we manufactured mixture for measuringphotoconductivity and elements applying to it.

[0126] After mixing polyester polymer produced in the above example 4and charge producer C₆₀ in Formula 4 of 99:1 by weight ratio, themixture is dissolved in organic solvent to make it 5-10% by weight. Andthe mixture was filtrated with injection filter to remove impurities.After dropping the filtered mixture into glass coated with two sheets ofITO electrode respectively, the mixture was heated to remove solvent.After putting together the said two sheets of glass to manufacture themixture layer with thickness of 100 μm, we connected currents to saidtwo ITO electrodes respectively to make elements. We inspected phaseisolation of the manufactured element at room temperature for 6 months.The result of electrical conductivity of the said element, which resultis shown in FIG. 2, was about 4 fold high than that of generally usedPVK-applied elements.

EXAMPLE 8 Manufacture of Photo-Refractive Mixture and Element forMeasuring Photo Refraction Property

[0127] In this example, we manufactured photo-refractive mixture formeasuring photo refraction and element applying to it.

[0128] After mixing polyester polymer produced in the above example 4,nonlinear-optical characteritic group in Formula 6 and charge producerC₆₀ of 64.5:35:1 by weight ratio, the mixture is dissolved in organicsolvent to make it 5-10% by weight. And the mixture was filtrated withinjection filter to remove impurities.

[0129] After dropping the filtered mixture into glass coated with twosheets of ITO electrode respectively, the mixture was heated to removesolvent. After putting together said two sheets of glass to manufacturethe mixture layer with thickness of 100 μm, we connected currents to thesaid two ITO electrodes respectively to make elements. We inspected thephase of this element at room temperature for 6 months. The element wasstabilized without phase isolation owing to rigid backbone 6 monthsafter manufacturing.

[0130]FIG. 3 is a graph showing the analysis result of XRD (X-RayDiffractometer) for the said manufactured photo-refractive mixture. Thegains factor of element manufactured in this example measuring withtwo-beam coupling was 200 cm⁻¹. At this time, laser used in two-beamcoupling was He—Ne of 633 nm, interval between two lights was 20 degreesand intensity of applied electrical field was 4.2 kV.

EXAMPLE 9 Photo-Breakage Effect

[0131] In this example, we inspected photo-breakage effect of photoelement containing photo-refractive mixture in the present invention.

[0132] On applying electrical field and irradiating light to elementmanufactured in the said example 8, it happened that over 65% ofirradiated light was dispersed to break the light. This phenomenonhappened faster with more stronger the intensity of light and morestronger intensity of electrical field. This phenomenon based upon thephoto refraction of the said element itself produced interior, by usingthis phenomenon properly, it can be used photo-breakage elements forpreventing damages by strong light. FIG. 4 is a graph showing themeasure results of photo-breakage effect for photo-refractive mixturesof the present invention.

[0133] It should be understood that various changes and modifications tothe presently preferred embodiments described herein will be apparent tothose skilled in the art. Such changes and modifications can be madewithout departing from the spirit and scope of the present invention andwithout diminishing its attendant advantages. It is therefore intendedthat such changes and modifications be covered by the appended claims.

What is claimed is:
 1. A Self-arrayed polymer with hole-carryabilitycomposed of the repeat-unit structure shown in formula 1 below: [Formula1]

wherein A is a chromophore (hole-carryable characteristic group), whichis selected from the compound in Formula 2 or Formula 3 below: [Formula2]

wherein R₁ is —O—(CH₂)_(q)— (q is an integer from 1 to 20),—S—(CH₂)_(m)— (m is an integer from 1 to 20),

 (n is an integer from 1 to 5) or

 (p is an integer from 1 to 5); and [Formula 3]

wherein R2 is —O—(CH₂)_(v)—O— (v is an integer from 1 to 20),—S—(CH₂)_(w)—S— (w is an integer from 1 to 20),

 (n is an integer from 1 to 5) or

 (p is an integer from 1 to 5): r is an integer from 3 to 300 aspolymerization degree X is selected from

M is a selected from 1) to 4) below as a co-monomer. 1)

 (wherein B is H, Cl, Br or CH₃) 2)

 (wherein said compound is 1,1′-, 2,2′-, 3,3′-, 4,4′-, 1,3′-, 1,2′-,2,3′-, 2,4′- or 3,4′-biphenyl series isomers); 3)

 (wherein said compound is 1,4-, 1,5-, 1.6-, 1,7-, 2,3-, 2,5-, 2,6- or2,7-naphthalene series isomers); and 4)

 (wherein Y is O, CH₂, SO₂, S,


2. A self-arrayed polymer according to claim 1, wherein said polymer hasa number average molecular weight of 2,000 to 240,000.
 3. Aphoto-refractive mixture using host-guest series making charge producerand electro-optical material dispersed as being medium of self-arrayedpolymer in claim
 1. 4. A photo-refractive material according to claim 3,wherein said charge producer is composed of the structure as belowFormula 4 or
 5. [Formula 4]

[Formula 5]


5. A photo-refractive material according to claim 3, wherein saidelectro-optical material is composed of the structure as below Formula6. [Formula 6]

(wherein R₁ is (C₁-C₁₀) alkyl, (C₁-C₁₀) alkyl substituted with hydroxylgroup to terminal end or (C5-C10) cycloalkyl; R₂ is nitro group ordicyanovinyl group)